Glass and glass powder mixture and use thereof for the production of a glass ceramic

ABSTRACT

A glass, in particular a glass powder, is fused from a starting mixture containing 38 wt % to 48 wt % SiO 2 , 15 wt % to 19 wt % Al 2 O 3 , 4.5 wt % to 11 wt % TiO 2 , 0 wt % to 1.5 wt % Na 2 O, 0 wt % to 1.5 wt % K 2 O and 23 wt % to 30 wt % CaO. In addition, a glass powder mixture contains a first such glass powder having a mean particle size of 150 μm to 250 μm and a second such glass powder having a mean particle size of less than 100 μm, in particular from 10 μm to 70 μm, as well as carbon black powder and an organic binder. This glass or glass powder mixture is especially suitable for producing a glass ceramic, in particular in the form of a resistor seal and/or a gas-tight glass ceramic solder in a spark plug.

[0001] The present invention relates to a glass, in particular a glass powder and a glass powder mixture, as well as their use to produce a glass ceramic which can be used in particular as a resistor seal or ceramic solder in a spark plug.

BACKGROUND INFORMATION

[0002] German Patent Application 196 51 454 A1 describes a spark plug having an electrode connected across a terminal stud to an ignition line, with a resistor made of glass or a glass ceramic material having a high thermal stability being arranged between the electrode and the ignition line. In addition, it is known from this related art that the glass powder used as the starting material to produce this burn-off resistor may be metallized at the surface in a currentless operation.

[0003] The insulator base of novel spark plugs having a platinum center electrode develops temperatures up to 950° C. Because of this temperature, options must be developed for contacting the center electrode, for producing a protruding burn-off resistor and for contacting this protruding burn-off resistor so that all these elements can tolerate an operating temperature of at least 900° C. for more than 2000 h. At the same time, the process temperature in production of the spark plug must not exceed 950° C. to prevent oxidation or deformation of the stud material.

[0004] In the past, the center electrode has usually been contacted with a contact pin by diffusion welding. However, the problem then occurred that the coefficient of thermal expansion of the contact pin material was often not adequately adapted to the surrounding insulator, so that unwanted stresses and defects occurred.

[0005] The object of the present invention was to provide a glass and a glass powder mixture produced with the help of this glass and suitable for producing a thermally stable glass ceramic which has high voltage strength at a low process temperature. This glass ceramic should then be suitable for use as a resistor seal and/or as a gas-tight ceramic solder in a spark plug.

ADVANTAGES OF THE INVENTION

[0006] The glass and the glass powder mixture according to the present invention have the advantage in comparison with the related art that they can be used to produce a glass ceramic which has high voltage strength at room temperature up to 20 kV/mm or at 800° C. up to 10 kV/mm. In addition, the coefficient of thermal expansion of this glass ceramic is approx. 6 ppm/K at approx. 100° C. to 200° C. and approx. 9 ppm/K at approx. 700° C. to 800° C., i.e., it is suitable for the aluminum oxide insulator material usually used in spark plugs.

[0007] In addition, the glass according to the present invention has a softening temperature E_(g) (determined dilatometrically) of approx. 720° C. to 820° C., so that it is possible to produce glass ceramic seals at temperatures of 850° C. to 950° C. It is especially advantageous that the refractory phases anorthite, wollastonite and titanite crystallize out in the process, so the resulting glass ceramic is then thermally stable to temperatures above 1000° C.

[0008] The glass powder mixture according to the present invention also makes it possible in an advantageous manner to produce a glass ceramic in the form of an electrically conducting glass ceramic solder which is suitable for contacting a center electrode or a burn-off resistor in a spark plug. This conductive ceramic solder is especially gas-tight and resistant to oxidation.

[0009] The glass ceramic produced from the glass or glass powder according to the present invention in the form of a resistor seal is also advantageously suitable for producing a resistor seal having a high thermal stability.

[0010] Thus, on the whole, the glass and the glass powder mixture according to the present invention make it possible to produce glass ceramic seals such as those needed in the production of spark plugs, for example, which have a higher thermal stability with no change in process temperature at the same time in comparison with the usual method.

[0011] Advantageous refinements of the present invention are derived from the measures characterized in the subordinate claims.

[0012] With regard to the high voltage strength and the process temperature, it is advantageous if the glass according to the present invention has a composition according to claim 3.

[0013] A composition according to claim 4 is especially advantageous with regard to the high voltage strength, process temperature and development of the refractory phases which develop in a heat treatment of this glass powder due to crystallization in at least some areas. This composition has especially good thermal stability and also has a coefficient of thermal expansion which is adapted especially well to that of aluminum oxide.

[0014] In addition, it is advantageous that the glass according to the present invention is also suitable for producing a glass ceramic seal having a low resistance, in that before the glass powder is fused and thus converted to a glass ceramic, it is provided with a surface metallization, in particular metallization with a metal having a high thermal stability such as platinum, palladium, nickel, tungsten or an alloy of these materials at least partially or at least in some areas. This surface metallization is preferably produced by a currentless method, such as that known from German Patent Application 196 51 454 A1.

[0015] Finally, the zirconium dioxide added to the glass powder mixture according to the present invention or the added mullite is advantageously suitable for adjusting the coefficient of thermal expansion of the glass ceramic ultimately obtained.

[0016] Embodiments

[0017] First, a glass is fused in a known manner from a starting mixture having a composition according to the table below. To do so, the individual components of the starting mixture are used first as a powder and mixed for the various glasses indicated as embodiments and then fused at temperatures of typically more than 1500° C. to form a glass. Components of the starting mixture (wt %) Glass 1 Glass 2 Glass 3 Glass 4 Glass 5 SiO₂ 46.5 47.9 45.6 45.0 45.0 Al₂O₃ 17.2 17.7 16.9 17.0 17.0 CaO 25.3 26.1 24.8 28.0 28.0 Na₂O 0.5 1.0 1.0 0.5 0 K₂O 0.5 1.0 1.0 0.5 0 TiO₂ 10.1 6.2 9.8 9.0 9.0 Li₂O 0 0 1.0 0 1.0 α × 10⁻⁶ (K⁻¹) 7.5 8.0 8.8 8.3 8.4 T_(g) (° C.) 758 743 678 753 700 E_(g) (° C.) 792 775 717 786 742

[0018] The information in the preceding table concerning the composition of the starting mixture is given in percent by weight (wt %) in each case. In addition, the respective coefficient of thermal expansion α in the temperature range from 100° C. to 500° C. is also given for the fused glass. It should also be pointed out that in addition to the components indicated above in the various starting mixtures, other typical glass components such as MgO, BaO, ZrO₂ and Fe₂O₃ may also be present in minor amounts, but their total amount should not exceed 2 wt %.

[0019] Finally, the term T_(g) is understood to refer to the measured glass transition temperature of the resulting glass, while E_(g) is the dilatometric softening point.

[0020] Glass 4 is an especially preferred embodiment with regard to the properties of the resulting glass in the preceding table.

[0021] The glass obtained after melting is then milled to form a glass powder and can then be used, for example, for further processing to form a glass ceramic resistor seal having a high resistance or a glass ceramic solder having a low resistance in a spark plug.

[0022] To do so, the glass powder is first processed further in the manner known from German Patent Application 196 51 454 A1 and is finally converted to a glass ceramic at a process temperature of 850° C. to 950° C., whereupon the refractory phases anorthite, wollastonite and titanite crystallize out, so that the resulting glass ceramic is thermally stable up to temperatures above 1000° C. The electric resistance of such a resistor seal in the form of a burn-off resistor in a spark plug is typically more than 1 kΩ.

[0023] To obtain an electrically conducting glass ceramic solder from the glass powder produced by the method described above, it may also be provided with a surface metallization, in particular with a surface metallization in the manner known from German Patent Application 196 51 454 A1. To do so, after seeding, a currentless surface metallization of the glass powder is performed with a metal that is stable at high temperatures, such as platinum, palladium, nickel, tungsten or an alloy of these materials. The thickness of this surface metallization is typically 0.5 nm to 10 nm, and the metallizing glass powder having a mean particle size of less than 250 μm, in particular 10 μm to 70 μm, is preferably used. The glass powder thus provided with a surface metallization can then be melted again at a process temperature of 850° C. to 950° C. to form a glass ceramic.

[0024] The resulting glass ceramic is suitable as a glass ceramic solder, for example, for bonding a metallic contact pin or a stud in a spark plug, for example, to a glass ceramic burn-off resistor produced in the manner described above. The electric conductivity of such a glass ceramic solder is determined by the surface metallization of the powder used, which forms in fusion a metal phase, in the form of metal paths which carry the electric conductivity of the glass ceramic solder, which is embedded in a glass ceramic matrix, in particular designed in the form of a network.

[0025] An alternative embodiment for producing an electrically conductive glass ceramic solder provides for two different glass powders to be milled from the glasses described above, e.g., glass 4, the first glass powder having a mean particle size of 50 μm to 250 μm and the second glass powder having a mean particle size of less than 100 μm, in particular from 10 μm to 70 μm. In addition, a carbon black powder having a mean particle size of 200 nm to 2 μm, in particular from 400 nm to 600 nm is provided and an organic binder is prepared from carboxymethylcellulose and dextrin to which water is added as the solvent. Finally, a zirconium dioxide powder having a mean particle size of less than 100 μm and a mullite powder having a mean particle size of less than 100 μm are also prepared.

[0026] Then the first glass powder is mixed with the second glass powder, the carbon black powder, the binder, the zirconium dioxide powder and the mullite powder. This mixture is prepared so that it contains an amount of 40 wt % to 58 wt % of the first glass powder, an amount of 3 wt % to 13 wt % of the second glass powder, an amount of 0.9 wt % to 2.5 wt % of the carbon black powder, an amount of 10 wt % to 37 wt % of the zirconium dioxide powder, an amount of 8 wt % to 13 wt % of the mullite powder, and an amount of 0.6 wt % to 4 wt % of the binder, all of these amounts in wt % being based on a solvent-free glass powder mixture. The total amount of solvent in the resulting glass powder mixture is 12 to 40 vol %, especially 22 to 37 vol %. Thus on the whole, after mixing the components indicated above, this yields a glass powder mixture in which the powder particles of the first glass powder are provided at least largely with a compound of the other components.

[0027] The resulting glass powder mixture is then subjected to a heat treatment at a process temperature of 850° C. to 950° C., whereupon the glass powders used crystallize in at least some areas or partially and the refractory phases anorthite, wollastonite and titanite are formed again.

[0028] Thus on the whole, a glass ceramic in the form of a seal is formed, containing a glass ceramic matrix having a carbon phase in the form of a network embedded in the matrix and formed by pyrolysis of the carbon black powder and organic binder added to the glass powder mixture.

[0029] Such a glass ceramic is also especially suitable as a glass ceramic solder in production of a spark plug. 

What is claimed is:
 1. A glass, in particular a glass powder fused from a starting mixture containing 38 wt % to 48 wt % SiO₂, 15 wt % to 19 wt % Al₂O₃, 4.5 wt % to 11 wt % TiO₂ and 23 wt % to 30 wt % CaO.
 2. The glass according to claim 1, wherein at least one alkali metal oxide, in particular lithium oxide, potassium oxide or sodium oxide, is added to the starting mixture in an amount of up to 1.5 wt % each.
 3. The glass according to claim 1 or 2, wherein the starting mixture is composed of 43 wt % to 48 wt % SiO₂, 16.5 wt % to 18 wt % Al₂O₃, 6 wt % to 10.5 wt % TiO₂, 0.3 wt % to 1.2 wt % Na₂O, 0.3 wt % to 1.2 wt % K₂O and 24.5 wt % to 28.5 wt % CaO.
 4. The glass according to claim 1, wherein the starting mixture is composed of 45 wt % SiO₂, 17 wt % Al₂O₃, 9 wt % TiO₂, 0.5 wt % Na₂O, 0.5 wt % K₂O and 28 wt % CaO.
 5. The glass according to at least one of claims 1 through 4, wherein the glass powder is provided at least partially and in at least some areas with a surface metallization, in particular a metallization with a metal having high thermal stability, such as platinum, palladium, nickel, tungsten or an alloy of these materials.
 6. The glass according to claim 5, wherein the powder has a mean particle size of less than 250 μm, in particular from 10 μm to 70 μm, and the thickness of the surface metallization is 0.5 nm to 10 nm.
 7. A glass powder mixture having a first glass powder according to at least one of claims 1 through 4, having a mean particle size of 150 μm to 250 μm, and a second glass powder according to at least one of claims 1 through 4, having a mean particle size of less than 100 μm, in particular from 10 μm to 70 μm, and a carbon black powder and an organic binder.
 8. The glass powder mixture according to claim 7, wherein the carbon black powder has a mean particle size of 200 nm to 2 μm, in particular from 400 nm to 600 nm.
 9. The glass powder mixture according to claim 7 or 8, wherein the organic binder contains carboxymethylcellulose and dextrin, and water is added to the binder as the solvent.
 10. The glass powder mixture according to at least one of claims 7 through 9, wherein zirconium dioxide is added to the mixture, in particular as a powder having a mean particle size of less than 100 μm.
 11. The glass powder mixture according to at least one of claims 7 through 10, wherein mullite is added to the mixture.
 12. The glass powder mixture according to at least one of claims 7 through 11, wherein the mixture contains an amount of 40 wt % to 58 wt % of the first glass powder, an amount of 3 wt % to 13 wt % of the second glass powder, an amount of 0.9 wt % to 2.5 wt % carbon black powder, an amount of 10 wt % to 37 wt % zirconium dioxide, an amount of 8 wt % to 13 wt % mullite and an amount of 0.6 wt % to 4 wt % binder, all amounts in wt % being based on a solvent-free glass powder mixture.
 13. The glass powder mixture according to claim 12, wherein the amount of the solvent in the glass powder mixture is 12 to 40 vol %, especially 22 vol % to 37 vol %.
 14. A use of the glass powder mixture or the glass powder according to at least one of claims 5 through 13 for producing a glass ceramic, in particular a resistor seal and/or a gas-tight glass ceramic solder in a spark plug. 